Disazo dyes



United States PatentO DIQAZO DYES James F. Fecmau, West Reading, Pa.,assignor to Althouse Chemical Co., Worcester, Mass, a corporation ofMassachusetts No Drawing. Application July 9, 1956, Serial No. 596,442

8 Claims. (Cl. 260153) This invention relates to a new class of disazocompounds, especially useful as dyes for reasons mentioned more fullyhereinafter.

The new disazo compounds have the following structure:

wherein x is a whole number greater than 1 and less than 4; R1 is aradical selected from the group consisting of I I S0311 HOaS R2 is aradical selected from the group consisting of Y is a radical selectedfrom the group consisting of -CO, -CO-CH=CR3-CO- (wherein Ra is aradical selected from the group consisting of -H, Br, --Cl and -CHa),and

\ l HNRl (wherein R4 is a radical selected from the group consisting ofH, -lower alkyl, --phenyl and -lower alkylated phenyl).

The dotted linkages wherever shown indicate bond- Patented June 11, 1957ing of substituent groups to ring nuclei at any available positions inthe entire ring structure providing stable linkages.

The triazole structure of the naphthotriazole moiety is sometimesillustrated in the following ways:

and

Such compounds can be prepared as set forth in the followingillustrative examples. In these examples, unless otherwise indicated,parts are by weight, temperature is given in degrees Centigrade, andpercentages are percentages by weight.

Example I A solution is prepared from 18.4 parts of benzidine, 30 partsof 30% hydrochloric acid and 200 parts of water at The solution isallowed to cool to 60; 20 parts of 30% hydrochloric acid are added; andthe resultant suspension of benzidine dihydrochloride is cooled to 10 bythe addition of ice. Then 14 parts of sodium nitrite, as a 30% solutionin water, are added during five minutes, the temperature beingmaintained at 10 by further addition of ice as needed. After completionof the diazotization, the excess of nitrous acid is removed by additionof sulfamic acid, in amount sufiicient to produce a negative test whenthe clear tetrazonium salt solution is spotted on starch-iodide paper.

Ice is then added to the solution to lower the temperature to 0, and 30parts of sodium bicarbonate are sifted into the solution. 25 parts ofpyridine are added. followed immediately by a solution prepared from 42parts of 8-amino 1, 3,G-naphthalenetrisulfonic acid, parts of water andsufiicient sodium carbonate to raise the pH of the solution to 7.5.Coupling is allowed to proceed at 05 for 16 hours. The pH of the mixtureis then lowered to 5.5 with 25 parts of glacial acetic acid, and asolution of 12 parts of m-toluidine in 25 parts of water and 12 parts of30% hydrochloric acid is added. The temperature of the coupling isallowed to rise to 20 during three hours. The coupling mixture is thentreated with 28 parts of sodium hydroxide and the temperature is raisedto 90 and held at this temperature during the addition of 50 parts ofcrystalline copper sulfate pentahydrate, and for one hour additional.100 parts of 30% hydrochloric acid are then added, and the precipitatedhydrochloride of the intermediate of the formula 3 is filtered. Thisamino-azo compound is further purified by dissolving it in 1500 parts ofwater with the addition of sodium hydroxide to raise the pH to 11,heating to 95, adding 30 parts of activated charcoal and 50 parts of asiliceous filtering aid, filtering, and salting the amino-azo compoundfrom solution by addition of sodium chloride. After filtering theintermediate, it is reacted in aqueous solution at pH 6.5-7.5 and at 25to 50 with phosgene until free amino group is no longer present. Theresultant new dye is precipitated from solution by addition of sodiumchloride, filtered Example III OCH:

sour note 0 It is a red-brown powder which dyes cotton and regeneratedcellulose in orange shades of excellent fastness to light and toWashing.

Example IV and dri d, It h th fo ul 69.5 parts of the amino-azo compoundused to prepare 1L (13H: -OO

HOsS- SO1H 2 and is a yellow-brown powder which dyes cotton andregenerated cellulose in clear yellow shades of excellent fastness tolight and to washing.

Example II 68.3 parts of the compound of the formula SOzH H038 HOaS SOsH

the dye in Example I are reacted with 7.65 parts of fumaroyl chloride.While vigorously stirring the dye intermediate solution, a solution of7.65 parts of fu- F maroyl chloride in 40 parts of benzene, and a sodium(prepared by coupling diazotized 4-amino-4'-nitro-2,2- ness to light andwashing. It has the formula stilbenedisulfonic acid withG-amino-1,3-naphthalenedisulfonic acid, oxidizing the nitro-amino-azocompound thus produced with cupric ammonium hydroxide solution to thecorresponding nitro-naphtho (1,2)triazole, and reducing the nitro groupwith iron powder in dilute acetic acid solution) are diazotized directlyin aqueous solution, and coupled at pH 3.5-4.5 with 10.7 parts ofm-toluidine. The amino-azo compound thus produced is then reacted withphosgene in aqueous solution at pH 6.5-7.5 and to until free amino groupis no longer present. The new dye which precipitates is filtered anddried. It is an orange-brown powder which dyes cotton and regeneratedcellulose in yellow shades of excellent fastness to light and towashing. It has high tinctorial strength and has the formula notw 0.11no. HI 01 69.5 parts of the amino-azo compound used to prepare the dyeof Example I are dissolved in neutral aqueous solution at 40. Whilestirring vigorously, 9.2 parts of cyanuric chloride in 50 parts ofacetone and another solution of sodium carbonate are added slowlydropwise to the dye intermediate solution, the sodium carbonate solutionbeing added in sufficient amount to keep the reaction at pH 6.5-7.5.After the cyanuric chloride solution has been added completely, thetemperature is maintained at 40 for 30 minutes and the pH maintained at6.5-7.5. Then the temperature is raised to and 4.7 parts of aniline areadded. The temperature is maintained at 90 for an additional hour. Thenew dye,

Example V thus produced, is separated from solution by salting, Whencyanuric chloride is used as the condensing refiltered and dried. Thenew dye produced is a yellowagent the third chlorine can be replaced byreacting the brown powder which dyes cotton and regeneratedcellucondensation product with aniline as described in Example lose inyellow shades of excellent fastness to light and V or by the use ofother reagents such as ammonia, lower washing. It has the formula 5alkyl amines or lower alkylated anilines.

N CH, 3 P- N s H015 302B 2 HNCgHs Example VI Equivalent amounts of othercondensing agents such as fumaroyl bromide or dichlorides or dibromidesof maleic, mesaconic, citraconic, bromofumaric, chlorofumaric,chloromaleic or bromomaleic acid can be used in lieu of The disazocompound (0.5 part), obtained according to Example II, is dissolved in adyebath which contains 2000 parts of water. Cotton (100 parts) isentered at 40 50o; the bath is heated to within 30 minutes; on fumartiylchlorlde to elfect azo condensations of the type A genera 1y illustratedby Example IV. parts of sodlum qhlonde are and dyemg 15 These new disazocompounds are water soluble and Performed f minutes more at thlstemperature are particularly useful as substantive dyes to impart yel-The l 15 then wen'exhflusted of color T dyed low and orange shades tocellulosic fibers. When used as 15 "used Cold and dned- The Cotton dyeda dyestuffs, they have been found to possess an excellent reddish-yellowshade of excellent fastness to light and 25 amnity for cellulose; theyShow outstanding dyging prop very good f' to Washmgerties; the colorsare unusually fast to light and the dyedyed fabllc, when afmrtreated Wureaformalde ings have outstanding wash-fastness. The wash-fastness hyde1n the usual manner well-known 1n the trade, Sh W and light-fastness ofthe colors are not adversely affected fnariiedly mcreasfid fastness toWashlng Wllh no decrease by conventional aftertreatments with heathardenable 1n llght fasmess- 3Q resins used in various fabric finishingprocesses to impart In the various compounds of the Present invention,desirable properties or effects to the fabric (e. g., stabililhBSLllfOHlC acid radicals C311 3% Substitlltd at different ationcrease-proofing durabilizing mechanical finish positions of thenaphthotriazole nuclei than those shown ff m) d conventional d fa t iagents in the illustrative examples- The number and position- (usuallycationic resinous materials or aminoaldehyde iflg 0f the Suifonic acidradicals Will depend 3; condensation products) used to increasewash-fastness of structure of the napththylamine sulfonic acid which isthe dyeings have a far less adverse effect on the lightinitially coupledwith the aminonitmal'yl 0F no y fastness of the dyes of this inventionthan on comparable compound; useful naphthylamine sulfonic acids includeyellow nd orange dyes heretofore a ilabl3-amino-l,5naphthalenedisulfonic acid, 3-amino-2,7- A rather strikingcharacteristic of these new disazo dyes naphthalenedisulfonic acid,4-amino-1,G-naphthalenediis their unusually high light-fastness eventhough the dye sulfonic, acid, 5-amino-2,7-naphthalenedisulfonic acidmolecule is not metallized" (i. e., does not contain6-amino-l,3-naphthaler1edisulfonic acid, 7-amino-1,3- copper). Thereforethese dyes can be used in many innaphthalenedisulfonic acid,8-amino-l,6-naphthalenedistances where the combination of wash andlight-fastsulfonic acid, 7-amino-l,3,G-naphthalenetrisulfonic acid,nesses are desirable but where metallized dyes are un-7-amino-2,4,6-naphthalenetrisulfonic acid, 8-amino-1,3,5- suitable, e.g., the dyeing of rubber-backed fabrics. naphthalenetrisulfonic acid,S-amino-l.,3,6-naphthaleneclaim: t i lf i acid, m 1. A disazo compoundhaving the following structure Useful dyes having good light-fast andwash-fast char acteristics can be prepared from the di and tri sulfonic4\ i acids of the naphthylamines. However, when the dyes N Y are to beapplied to fibrous materials containing a mixture (11035). of syntheticssuch as nylon or acetate and cellulosic fibers it is preferred to have 3sulfonic acid radicals in the naph- 2 thotriazole nucleus when R1 of thegeneral structural wh rei formula is x is a whole number greater than 1and less than 4;

3 G R1 is a radical selected from the group consisting of and 2 sulfonicacid radicals in the naphthotriazole nucleus when R1 of the generalstructural formula is 03K Haas BOsH HOAS R2 is a radical selected fromthe group consisting of and since the lower sulfonic acid compounds tendto stain nylon and acetate.

When fumaroyl chloride and cyanuric chloride are used C to condense theamino-azo intermediates which form I yellow dyes, the dyes so producedtend to be somewhat greener than when the same azo intermediates areconand densed with phosgene. Cyanuric chloride is highly desirable as acondensing reagent for the azo compounds because it permits theformation of unsymmetrical dye molecules and in this way it is possibleto vary the shade of the color and the dyeing properties of thedyestutf. A

7 Y is a radical selected from the group consisting of 2. A disazocompound according to claim 1 wherein x CO, C0-CH=CR;CO, and is 2 whenR1 is N -on=onQ g C 1!: ii 5 0 H H0 8 \C/ I I 3. A disazo compoundaccording to claim 1 wherein x is 3 when R1 is Rs being a radicalselected from the group consisting of 10 H, Br, --Cl, and CHs and R4being a radical selected from the group consisting of H, lower alkyl,phenyl and lower alkylated phenyl. 4. The compound N H: =CO

H0; sons 5. The compound Nil? 0 n=0 HQN=NQNH- Hols N soln H0. H.

OI -l2 6. The compound eg, H=OH N=NQ NH Ems N soln H015 H. =00

7. The compound 8. The compound Rois N IIQOQN=N HO S SOaH ReferencesCited in the file of this patent UNITED STATES PATENTS 820,052 Kirchhoffet a1. May 8, 1906 2,004,250 Schindhelm et a1 June 11, 1935 2,270,478Schmid Ian. 20, 1942 2,385,862 Keller Oct. 2, 1945 2,673,198 GrandjeanMar. 23, 1954

1. A DISAZO COMPOUND HAVING THE FOLLOWING STRUCTURE